Textile treatment process



United States Patent 2,990,298 TEXTILE TREATWNI' PROCESS James Albert Moyse and Gerald Williams, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed June 9, 1958, Ser. No. 740,522 Claims priority, application Great Britain June 2.4, 1957 6 Claims. (Cl. 117-1395) This invention relates to a textile treatment process, more particularly for the production of finishes which possess improved resistance to wet treatments.

It is known to apply finishing agents to textile materials in order to impart to the textile materials certain desirable properties, for example stifiness or a full handle or, alternatively, a soft handle. These finishing agents, however, are frequently water-sensitive materials, with the result that the finishes possess little resistance to water or wet treatments, and the finishing agent is readily removed from the textile material.

We have now found that these disadvantages may be overcome, and that finishes may be produced which are resistant to wet treatment, when water-sensitive finishing agents are used in conjunction with a monoor di-halogeno-l :3 :S-triazine.

Thus according to our invention we provide a process for the production on textile materials of finishes possessing improved resistance to wet treatments which comprises applying to the said textile materials a water-sensitive finishing agent and a monoor di-halogeno-l:3:5- triazine.

The water-sensitive finishing agent for use in the process of our invention may serve for example as a binder, filling agent or softening agent, and as examples of such agents there may be mentioned proteinaceous materials for example casein and gelatin; high molecular weight polyhydroxy compounds for example starches, starch ethers, dextrins, cellulose ethers and polyvinyl alcohol; and also water-soluble or water-insoluble amines, of which the latter are conveniently applied in the form of water-soluble salts with mineral or organic acids. Particular examples of suitable amines for the purpose of the present invention include long-chain aliphatic amines for example octadecylamine, alkylated arylamines containing a long aliphatic carbon chain in the molecule, for example 4-octadecylaniline and 4-octadecylphenylbiguanide, and the rection products of long-chain aliphatic carboxylic acids with polyalkylene polyamines.

In order to enhance the effect obtainable by the process of our invention, it is in general preferred to use the Water-sensitive finishing agent and the monoor di-halogeno-1z3z5-triazine in conjunction with an alkali. By this means the durability of the final finish of the textile material may be considerably improved, especially when the finishing agents are polyhydroxy compounds.

The monoand di-halogeno-l:325-triazines suitable for use in the process of the present invention may be water-soluble or water-insoluble, colourless or coloured. I

Thus for example there may be mentioned Water-insoluble compounds in which alkyl, cycloalkyl, aralkyl or aryl groups are attached to the triazine nucleus, for example 2 methyl 4:6 dichloro 1:3:5 triazine, 2 phenyl 4:6-dichloro-l:3:5-triazine, or compounds in which an organic radical is attached to the triazine nucleus through a nitrogen, oxygen or sulphur atom, for example 2-anilino 4:6 dichloro 1:315 triazine, 2 B naphthoxy- 4:6 dichloro 1:3 :5 triazine and 2 (p methylphenylthio) -4 6-dichloro-l :3 :5 -triazine.

Water-solub1e halogeno-lz3r5-triazines which may be used in the process of our invention, include monoand di-halogeno-lz3z5-triazines which contain, attached to at least one of the carbon atoms of the triazine ring through a nitrogen, oxygen or sulphur atom, an organic radical carrying either a negatively charged solubilising group, such as a sulphonic or carboxylic group, or a positively charged solubilising group, such as a quaternary ammonium group. As specific examples of such compounds there may be mentioned 1:4-bis[(4-chloro-6-methoxy- 1:3:5-triazin-2-y1)-amino]-benzene-2-sulphonic acid, 6- chloro 2:4 bis (2 sulpho 4 met-hylphenoxy) 1 :3 :S-triazine, ,8- (4 6-dichloro-l :3 5-triazin-2-yl) amino ethane sulphonic acid, 1-(4z6-dichloro-1z3:S-triazin-Z-yl) aminobenzene-3-sulphonic acid, 2-(4 6-dichloro-l 3 :5- triazin-Z-yl)aminonaphthalene-6-sulphonic acid, 2-(4:6- dibromo 1:3:5 triazin 2 yl) aminonaphthalene 6 sulphonic acid, l-(4z6-dichloro-l:3:5-triazin-2-yl)amino- 8 hydroxynaphthalene-3:6 disulphonic acid, 1:4-bis [(4z6 dichloro 123:5 triazin 2 yl)amino]benzene- 2-sulphonic acid, l-amino-4- [4-( 4: 6-dichloro-1 3 :5- tn'azin 2 yl)amino 3 sulphoanilino] anthraquinone-ZzS-disulphonic acid, 1-(4 6-dichl0ro-l :3 :S-triazin- 2-yl)aminobenzene-4-carboxylic acid, 3-(4z6-dichloro- 1 :3 S-triazin-Z-yl)aminophenyltrimethylammonium bromide and 4-(4:6-dichlorol:3:5-triazin-2-yl)aminophenacyltrimethyl ammonium chloride.

The monoand di-halogeno-l13:5-triazi11es may be made in known manner. For example, those containing an organic radical attached to the triazine nucleus through a nitrogen, oxygen or sulphur atom may be made by reacting a compound containing at least one 1:3 :S-triazine ring, wherein there are halogen atoms attached to at least two carbon atoms of the triazine ring, with an amine, alcohol, phenol or mercaptan in such proportions that at least one halogen atom remains attached to the triazine ring. As starting materials for this purpose cyanuric chloride and cyanuric bromide are especially valuable.

As examples of alkalies which may be used, if desired, in the process of our invention there may be mentioned potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and mixtures thereof.

The finishing agent, the halogeno-triazine and any alkali employed may be applied to the textile material simultaneously or successively in any order. Preferably, the textile material is treated by a one-bath process with a single solution or suspension containing the finishing agent, the halogeno-triazine and optionally the alkali, or alternatively by a two-bath process in which any alkali used is in the second bath. Thus for example the textile material may be treated successively With two solutions or suspensions of which the first contains the finishing agent and the second contains the halogeno-triazine and any alkali employed or the first contains the halogenotriazine and the second contains the finishing agent and any alkali employed, or the first contains both the halogeno-triazine and the finishing agent and the second contains the alkali.

When the halogeno-t riazine is water-soluble it is convenient to employ it in the form of an aqueous solution. When the halogeno-triazine is insoluble in water, it is most conveniently employed in the form of an aqueous dispersion or suspension, which may be readily made by stirring or milling the triazine with a dispersing agent which may be anionic, cationic, or non-ionic, for example, a sulphated long-chain aliphatic alcohol, a long-chain quaternary ammonium salt or an ethylene oxide condensate of an alkyl phenol. Since some of the finishing agents, such as gelatine, casein, starches, cellulose ethers and polyvinyl alcohol, which are used in the process of our invention possess dispersing properties or can stabilise dispersions or suspensions, it is not essential when using such finishing agents simultaneously with the waterto employ a dispersing 7 room temperature or by heating below 100.C., after each stage of the treatment. The treated textile material is then heated at a temperature up to 150 C., preferably between 100 C. and 140 C., for a time up to 15 minutes, to eiiect more complete reaction of the halogenatriazine with the finishing agent and thereby enhance the fastness of the finish to wet treatments. The particular temperature, and time selected will depend upon the particular textile material to be treated. The treated textile material may be heated,.for example, by steaming, by passage over heated drying cylinders, by passage through a heated chamber or a bath of molten metal.

The proportion of monoor di-halogeno-l:3:5-tria.zine .to be applied to the textile material may be between 5% p and 100% by weight of the finishing agent employed.

.The finishing agent may be used'in quantities up to 20%, and usually between 0.1% and of the Weight of the textile material, but will depend to a considerable extent .on the particular textile material tobe treated and the finish to be achieved. When alkali is used the proportion may be between 1% and 300%, preferably between 5% and 100%, by weight of the finishing agent employed.

Textile materials which may be treated by the process of our invention include both natural and synthetic materials, for example cotton, viscose and other cellulosic materials, cellulose acetates, polyamides, polyesters and wool. These textile materials may be in any form, for example, fibres, filaments, yarns, fabrics and the like.

Thefinished textile materials treated according to the process of our invention posses the advantage that the finish possesses an improved fastness to wet treatments, for example washing. Thus, a more permanent modification of the handle of both natural and synthetic textile materials can be achieved than can normally be obtained by the use of the finishing agent alone. In the case of cellulosic materials, the treatments involving the use of polyhydroxy and proteinaceous materials are suitable for the production of window holland and bookcloth finishes and weftless tapes possessing excellent resistance to water.

The invention is illustrated but not limited by the following examples in which the parts and percentages are by weight: 1

Example 1 7.5 parts of sago starch are boiled in 100 parts of water until dissolved, and the solution is cooled to 20 C. 0.5 part of the sodium salt of 2-(4:6dicbloro-l:3:5- triazin-Z-yl)aminonaphthalene-G-sulphonic acid and 0.75 part of sodium bicarbonate are added and dissolved. A cotton limbric fabric is impregnated with the resulting solution and the wet pattern then heated at 110 C. for 8 minutes. The treated pattern is then washed in boiling soap solution. The pattern, when dried, possesses a fuller and firmer handle than a cotton limbric fabric which has been treated with sago starch alone and then subjected to the same washing treatment.

Example 2 lution.

stiffer than the untreated material and retains a considerable measure of this stiffness after washing in alkaline liquors.

Example 3 A wheat starch solution isprepared as described in Example 2. To the cold solution is added 0.75 part of the sodium salt of 1;4-bis-(4-chloro-6'methoxy-1z3z5-triazin-2-ylamino)benzene-Z-sulphonic acid and 1 part of sodium bicarbonate. A cotton limbric fabric is impregnated with this solution and the wet pattern then heated at 110 C. for 10 minutes, and finally washed in soap so- The treated pattern possesses a firmer handle than a cotton limbric fabric which has been treated with wheat starch alone and similarly washed.

Example 4 A cotton limbn'c fabric is impregnated with the wheat starch composition of Example 3 and dried at room temperature to an approximate moisture content of 10%. The fabric is glazed by passage through a heated calender with friction and then heated at 110 C. for 2 minutes. The pattern retains a considerable proportion of its glaze and stiifness on being subjected to a washing treatment.

, Example 5 10 parts of polyvinyl alcohol are dissolved in parts of water and to the cold solution is added, while stirring, 1 part of 2-;3-naphthoxy-4:6-dichloro-123:5-triazine and 1 part of sodium bicarbonate. A cotton limbric is impregnated with this composition and the wet pattern then heated at 120 C. for 7 minutes and finally Washed in'soap and soda solution. The treated fabric possesses an attractive, full handle, whereas a cotton limbric fabric treated with only the polyvinyl alcohol and subjected to the same washing treatment does not retain its initial fullness.

Example 6 When, in the procedure of Example 3, the sodium salt of 1 :4-bis (4-chloro-6-methoxy-1 :3 :5-triazin-2-yl) aminobenzene-Z-sulphonic acid is replaced by an equal weight of p dichloro cyanurylaminophenacyl trimethylammonium chloride a similar result is obtained.

Example 7 A composition comprising 10 parts of wheat starch, 5 parts of china clay, 0.1 part of the pigment Monolite Fast Scarlet RNV (Colour Index No. 12120) and 85 parts of water is prepared. To this composition is added 1 part of the sodium salt of 2-(4-z6-dichloro-1:325-triazin- 2-yl)aminonaphthalene-6-sulphonic acid and 1 part of sodium bicarbonate, while stirring. The mixture is then applied by means of a knife spreading machine to cotton wigan cloth in three coats, each of 0.003 in. thickness, with hot drying between coats. The coated fabric is calendered at 70 C- without friction and finally heated at "C. for 2 minutes. The resulting window holland finished pattern shows good resistance to water and to light sponging with warm soap solution, as shown by the retention of pigment. In contrast, a pattern which has been treated with a pigmented starch composition which is the same as that described above, except that the 4:6- dichloro-1:3:5-triazinyl compoundand sodium bicarbonate have been omitted, shows little resistance to such wet treatments.

Example 8 finished fabric shows improved resistance to wet treatments, as indicated by the retention of pigment, when compared with a pattern treated with a pigmented gelatin composition which is the same as that described above except that the 2p-naphthoxy-4z6-dichloro-l:3:5-triazine and sodium bicarbonate are omitted.

Example 9 A cellulose acetate satin fabric is impregnated at 30 C. with a solution of 10 parts of gelatin, 1 part of the sodium salt of 2-(4z6-dichloro-1z3:5-triazin-2-yl)aminm naphthalene-G-sulphonic acid and 1 part of sodium bicarbonate. The wet pattern is then heated at 110 C. for 10 minutes. The stiffened fabric resulting from this treatment retains a considerable measure of its stiffness after being washed in soap and ammonia solution.

Example 10 When, in the procedure described in Example 9, a nylon twill fabric is used instead of the cellulose acetate fabric a firm handle is conferred on the nylon, and this finsh possesses fastness to washing in soap and soda ash solution.

Example 11 A cotton limbric fabric is impregnated at 30 C. with a solution of 5 parts of gelatin and 1 part of the sodium salt of 2(4:6-dich1oro-1:3:5-triazin-2-yl)aminonaphtha- Iene-G-sulph'onic acid in 94 parts of water. The wet treated pattern is then heated at 10 C. for 10 minutes. The stiff finish conferred on the fabric possesses fastness to washing in soap and soda ash solution.

Example 12 A cotton wigan cloth is impregnated with a solution of 1 part of the sodium salt of 2- (4:6-dichloro-1:3:5-t1iazin-Z-yl) aminonaphthalene-6-sulplronic acid in 99 parts of Water, and dried at 40 C. The cloth is then impregnated with a solution of 5 parts of gelatin and 1 part of sodium bicarbonate in 94 parts of water and the wet pattern is heated at 120 C. for 7 minutes. A firm handle possessing durability to washing in soap and soda ash solution is imparted to the fabric.

Example 13 A cotton wigan cloth is impregnated with a dispersion of 2 parts of 4-octadecylaniline in 8 parts of acetic acid and 90 parts of water and dried at 50 C. The cloth is then impregnated with a solution of 2 parts of sodium [3 (4:6 dichloro 1:3:5 triazin 2 yl)aminoethane sulphonate in 98 parts of water, dried at 50 'C. and heated at 140 C. for 3 minutes. The treated cloth possesses a softer handle after washing in soap and soda ash solution than cloth treated only with the 4-octadecylaniline.

Example 14 A cotton wigan cloth is impregnated at 30 C. with a solution of 10 parts of gelatin, v1 part of the sodium salt of 1-amino-4-[4'-(4 6-d-ich1oro-1 :3 :5-triazin-2-yl) amino- 3'-sulpho-anilino]-anthraquinone-2:S-disulphonic acid and 2 parts of sodium bicarbonate in 87 parts of water, dried at 50 C. and heated at 115 C. for 8 minutes. The coloured pattern retains a considerable measure of its stiifness on being washed in soap and soda ash solution.

Example 15 A viscose stoekinette fabric is impregnated with a solution containing 0.9 part of the acetate salt of the reaction product of equimolar proportions of stearic acid and tetraethylene pentamine, and 0.9 part of sodium fl-(4z6-dichloro-l:3:5-triazin-2-yl)aminoethane sulphonate in 98 parts of water. The fabric is dried at 50 C., heated at C. for 7 minutes, and finally washed in soap and soda ash solution. The treated pattern retains a greater degree of softness than a similar fabic treated merely with the acetate salt of the reaction product of stearic acid and tetraethylene pentamine.

Example 16 A cotton wigan cloth is impregnated at 30 C. with a solution containing 10 parts of gelatin, 1 part of finely dispersed 2-p-naphthoxy-4 6-dichloro-1 :3 :S-triazine (dispersed in water by milling for several hours with 20% of its weight of an alkali metal salt of a long chain alkyl sulphate) and 1 part of sodium bicarbonate in 88 parts of water. The fabric is dried at 50 C. and then heated at C. for 3 minutes.

The stiff handle thus conferred on the fabric possesses fastness to washing in soap solution.

Example 17 A cotton flannelette fabric is impregnated with solution containing 0.25 part of the acetate salt of octadecylbigua-nide in 99.75 parts of water and dried at 50 C. It is then impregnated with a solution containing 0.25 part of sodium I-( 4 6-dichloro-1 3 5 -triazine-2-yl) aminobenzene-3- sulphonate in 99.75 parts of water, dried at 50 C. and heated at 150 C. for 3 minutes.

The fabric thus treated retains a greater measure of softness than a simlar pattern treated only with the octadecylbigu-ani-de acetate.

What we claim is:

1. A process for the production on textile materials of finishes possessing improved resistance to wet treatments which comprises applying to the said textile materials a water sensitive finishing agent and a triazine selected from the group consisting of mono and dihalogeno-1z3z5-triazine wherein the halogen atoms are attached to the carbon atoms inthe triazine ring.

2. P-rocms according to claim 1 wherein a water sensitive finishing agent and said triazine are applied in conjunction with an alkali.

3. Process according to claim 1 wherein the water sensitive finishing agent contains active hydrogen atoms selected from the class consisting of hydroxylic and amino active hydrogen atoms.

4. Process according to claim 1 wherein said triazine is free from chromophoric groups.

5. Process according to claim 1 wherein said triazine is water-soluble.

6. Process according to claim 1 wherein the textile material is heated after application of the water sensitive finishing agent and said triazine.

References Cited in the file of this patent UNITED STATES PATENTS 2,197,357 Widmer Apr. 16, 1940 2,220,508 Bock et a1 NOV. 5, 1940 2,270,841 Bock et a1 Ian. 27, 1942 2,301,509 Bock et a1 NOV. 10, 1942 2,654,720 Cohen et a1. Oct. 6, 1953 

1. A PROCESS FOR THE PRODUCTION ON TEXTILE MATERIALS OF FINISHES POSSESSING IMPROVED RESISTANCE TO WET TREATMENTS WHICH COMPRISES APPLYING TO THE SAID TEXTILE MATERIALS A WATER SENSITIVE FINISHING AGENT AND A TRIAZINE SELECTED FROM THE GROUP CONSISTING OF MONO AND DIHALOGENO-1:3:5-TRIAZINE WHEREIN THE HALOGEN ATOMS ARE ATTACHED TO THE CARBON ATOMS IN THE TRIAZINE RING. 